The pagodane route to dodecahedranes: highly functionalized, saturated and bis-unsaturated pentagonal dodecahedranes via SN2 cyclizations

Pinkos, Rolf; Melder, Johann Peter; Weber, Klaus; Hunkler, Dieter; Prinzbach, Horst

doi:10.1021/ja00069a015

Cited by 53 publications

(30 citation statements)

References 5 publications

(7 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…ϭ 35.3°). [6] The 9,9Ј,10,10Ј-tetradehydrodianthracene (10), Scheme 1 prepared more than twenty years ago, has one of the highest angles for symmetrically out-of-plane bent alkenes ( ex. ϭ 35.9°).…”

Section: Results From Assignments Semiempirical and Ab Initio Dft Camentioning

confidence: 99%

Synthesis, Structure, and Properties of Twofold Bridged Sesquinorbornenes

Griesbeck¹,

Deufel

Hohlneicher

et al. 1998

Eur. J. Org. Chem.

View full text Add to dashboard Cite

The twofold bridged sesquinorbornenes 2 and 6 were prepared using sequential [4 + 2] cycloadditions of benzoquinone with 1,5‐dihydropentalenes 1 and 5. These syntheses were improved using dilution conditions or a more reactive substituted benzoquinone. Results from semiempirical and ab initio DFT calculations indicated remarkably high pyramidalization angles (ϕ = 46‐47°) for the central C–C double‐bond atoms. The chemical reactivity with triplet and singlet oxygen, dimethyldioxirane and N‐methyl‐1,2,4‐triazoline‐3,5‐dione supports these structural assignments.

show abstract

Section: Results From Assignments Semiempirical and Ab Initio Dft Camentioning

confidence: 99%

Synthesis, Structure, and Properties of Twofold Bridged Sesquinorbornenes

Griesbeck¹,

Deufel

Hohlneicher

et al. 1998

Eur. J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…2,3,[5][6][7][8][9][10][11][12][13][14][15] It is also vital to theoretically investigate electrophilic addition reactions in order to prove such rules. Therefore, electrophilic addition reactions of bromine to tetracyclo [ structures and stabilities of electrophilic addition reaction intermediates (bridged, N-and U-type cations) as well as geometric and electron structure of homohipostrofene molecule.…”

Section: -34mentioning

confidence: 99%

“…In some cases, only the cross or the parallel bridged product is isolated, while in other cases both products are formed simultaneously. 2,3,[5][6][7][8][9][10][11][12][13][14][15] Recently Inagaki et al advanced a perturbation theory to interpret those cases where preferential cross bridging takes place. 16 While the orbital mixing effect must certainly be working when cross bridging occurs, a general theory must explain why and to what extent parallel addition takes place in other systems.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of Electrophilic Transannular Addition Reactions of Bromine to Face-to-Face (Juxtaposed) Double Bonds in Strained Polycyclic Hydrocarbons

Abbasoğlu

2017

ACSi

View full text Add to dashboard Cite

Transannular electrophilic addition reaction of halogens to face-to-face(juxtaposed) double bonded strained alkenes were theoretically investigated. General rules that allow us to stipulate the factors that direct the main steps of the energy hypersurface of reactions as well as the products were established. Direction of the reaction flow is determined by direction of intramolecular skeletal isomerisation of cyclic-bridged halogenium cation and isomerisation takes place to create a more stable skeletal structure. Stability of resultant skeletal structure is determined by the number of σ bonds between isolated double bonds of the alkene and bonding-type of double bonds (N-and U-type). When the number of σ bonds between double bonds of the alkene is three (m = 3), the reaction takes place to predominantly give an N-type product, and when four (m = 4), N-and U-type products are formed. Structure and stability of cation intermediates (bridged, N-and U-type cations) of electrophilic addition reaction of homohipostrofen molecule, whose double bonds were linked by three σ bonds, with bromine were investigated by DFT methods in detail. Also the addition reaction of endo,endo-tetracyclo[6.2.2.2 3,6 .0 2,7 ]tetradeca-4,9-dien molecule, whose double bonds were linked by four σ bonds, with bromine were investigated by quantum chemistry.

show abstract

“…Sterically, such additions should be more favorable in 2 than in correspondingly functionalized disecodienes 1 [11a], but less favorable than in the corresponding dodecahedradienes 3 [36]. It was due to its better accessibility [37] that diester 2b served as substrate in most of these experiments.…”

mentioning

confidence: 99%

“…To recall, 1b did not react with diazomethane, whilst 3b rapidly delivered the bis-pyrazolo-fused derivative [37].…”

mentioning

confidence: 99%

Secododecahedradienes - Syntheses, Reactivity, in-Plane Homoconjugated 3C/2e Cations, 4C/3e Radical Cations, andσ-Bishomoaromatic 4C/2e Dications?

Reinbold

Bertau

Voss

et al. 2001

HCA

Self Cite

View full text Add to dashboard Cite

Edgar Heilbronner in alter Verbundenheit (H. P.; H.-D. M.) zum 80. Geburtstag Secodecahedradiene 2a, featuring very proximate, perfectly syn-periplanar and significantly pyramidalized CC bonds, was synthesized as testing object for in-plane(s)-homoconjugational electron delocalization, starting from the available pagodane 15b. The response of 2a (and in part its diester 2b) ± in p,p-distance (average 3.08 ), olefinic pyramidalization (average 26.98), and p,p-split (PE, 1.15 eV) intermediate between disecododecahedradiene 1a and 1,16-dodecahedradiene 3a ± to selected 4p-reagents, electrophiles, and radicals was explored experimentally and by calculations. Intriguing multistep reaction sequences attest to the ease of competing stabilization pathways for the 3C/2e in-plane homoconjugated cationic intermediates. PE, CV, and ESR measurements and calculations (DFT) characterize the radical cation generated from 2a as in-plane homoconjugated 4C/3e-species 2a. , persistent in a Freon matrix, but only very shortly existent in solution (CIDNP). Consequently, NMR control of the two-electron oxidation in SbF 5 /SO 2 ClF did not disclose the s-bishomoaromatic dication 4C/2e (see 2a 2 ), but a bis-allylic dication 75 as persistent species. In support of 2a 2 as intermediate, evidence is presented for very limited kinetic protection offered by the secododecahedral framework to through H-cage s-homoconjugated cations.

show abstract

The pagodane route to dodecahedranes: highly functionalized, saturated and bis-unsaturated pentagonal dodecahedranes via SN2 cyclizations

Cited by 53 publications

References 5 publications

Synthesis, Structure, and Properties of Twofold Bridged Sesquinorbornenes

Synthesis, Structure, and Properties of Twofold Bridged Sesquinorbornenes

Theoretical Investigation of Electrophilic Transannular Addition Reactions of Bromine to Face-to-Face (Juxtaposed) Double Bonds in Strained Polycyclic Hydrocarbons

Secododecahedradienes - Syntheses, Reactivity, in-Plane Homoconjugated 3C/2e Cations, 4C/3e Radical Cations, andσ-Bishomoaromatic 4C/2e Dications?

Contact Info

Product

Resources

About